CN117613227A - Double-carbon modified ferro-manganese-based mixed phosphate microsphere material and preparation method and application thereof - Google Patents
Double-carbon modified ferro-manganese-based mixed phosphate microsphere material and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 239000004005 microsphere Substances 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 63
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 28
- 239000010452 phosphate Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000011572 manganese Substances 0.000 claims abstract description 56
- 239000011734 sodium Substances 0.000 claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 9
- 239000002356 single layer Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims abstract description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PZQNFVCVNORNPG-UHFFFAOYSA-M [Na+].OP(O)([O-])=O.OP(O)(=O)OP(O)(O)=O Chemical compound [Na+].OP(O)([O-])=O.OP(O)(=O)OP(O)(O)=O PZQNFVCVNORNPG-UHFFFAOYSA-M 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- -1 carbon modified iron-manganese Chemical class 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 230000001351 cycling effect Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a double-carbon modified ferro-manganese-based mixed phosphate microsphere material, and a preparation method and application thereof. The microsphere material comprises carbon layer coated ferromanganese based mixed sodium pyrophosphate microspheres and reduced graphene oxide, wherein the reduced graphene oxide network is coated and connected with the carbon layer coated ferromanganese based mixed sodium pyrophosphate microspheres. The preparation method comprises the following steps: adding a sodium source and a phosphorus source into a carbon source solution, adding an iron source and a manganese source to obtain a transparent clear solution, adding a single-layer graphene oxide dispersion liquid, uniformly mixing, granulating by a spray dryer to form a precursor, and calcining. When the obtained microsphere material is used as a positive electrode material of a sodium ion battery, the circulation stability of the material is ensured, the working voltage is effectively improved, and the microsphere material has high reversible specific capacity, good circulation stability and excellent multiplying power performance; meanwhile, the preparation is simple, the required raw materials are green, safe, low in cost and easy to obtain, the method is simple, the yield is high, the uniformity of the product is good, and the market popularization is facilitated.
Description
Technical Field
The invention belongs to the field of nano materials and electrochemistry, and particularly relates to a double-carbon modified ferro-manganese-based mixed phosphate microsphere material, and a preparation method and application thereof.
Background
In the background of global energy shortage and increasing demand, the development of new energy and the protection of the environment are the subjects of the current social development. Sodium Ion Batteries (SIBs) are considered to be a suitable energy storage device because of their abundant production resources and low cost. The lithium ion battery is the most widely used secondary battery at present, however, with the rapid increase of the demand, the development of the lithium ion battery is severely restricted by the reserve of lithium metal, and the development of a novel secondary battery to replace the lithium ion battery becomes a popular research direction. Sodium ion batteries are receiving a great deal of attention for their inexpensive and readily available raw materials, high safety, and good performance. The sodium resource reserves are rich, the distribution is wide, the cost is low, and the development bottleneck does not exist; the working principle of the sodium ion battery is similar to that of the lithium ion battery, and the sodium ion battery can be compatible with the existing production equipment of the lithium ion battery; the sodium ion battery has excellent multiplying power performance, high and low temperature performance, no fire or explosion in safety test and good safety performance. Sodium ion batteries are therefore one of the most promising energy storage technologies in the post-lithium era, and their progress depends to a large extent on the development of compounds with rapid deintercalation reaction structures of sodium ions. In addition, large Scale Energy Storage Technology (LSEST) is very important for the development and utilization of new energy.
The traditional sodium ion battery phosphate anode material has poor conductivity and low energy density, so that the practical application is severely limited. The research of V (vanadium) element in phosphate materials is very extensive, however, the stable voltage platform of V is limited, the toxicity is high, the stable theoretical specific capacity is low, the price is gradually increased year by year, and the commercial requirement of large-scale energy storage is difficult to meet, so that people are promoted to adopt other transition metal elements with higher working voltage, rich reserve and low price to replace V so as to obtain the high specific energy, low cost and environment-friendly anode material.
Disclosure of Invention
The invention aims to provide a double-carbon modified ferro-manganese-based mixed phosphate microsphere material, and a preparation method and application thereof. When the microsphere material is used as a positive electrode material of a sodium ion battery, the cycling stability of the material is ensured, the working voltage is effectively improved, and the microsphere material has high reversible specific capacity, good cycling stability and excellent multiplying power performance; meanwhile, the preparation is simple, the required raw materials are green, safe, low in cost and easy to obtain, the method is simple, the yield is high, the uniformity of the product is good, and the market popularization is facilitated.
In order to solve the technical problems, the invention adopts the following technical scheme:
the double-carbon modified ferromanganese-based mixed phosphate microsphere material comprises ferromanganese-based mixed phosphate sodium pyrophosphate microspheres coated by a carbon layer and reduced graphene oxide, wherein the reduced graphene oxide is coated by a network and is connected with the ferromanganese-based mixed phosphate sodium pyrophosphate microspheres coated by the carbon layer; the chemical formula of the ferromanganese-based mixed sodium pyrophosphate phosphate is Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 )。
According to the scheme, the diameter of the double-carbon modified ferro-manganese-based mixed phosphate microsphere material is 1-10 mu m.
According to the scheme, the carbon content of the double-carbon modified ferro-manganese-based mixed phosphate microsphere material is 10-13%.
According to the scheme, the addition amount of the raw material single-layer graphene oxide of the reduced graphene oxide is 2-5% of the mass of the double-carbon modified ferro-manganese-based mixed phosphate microsphere material; the carbon source addition amount of the carbon coating layer is 1-1.5 times of the total molar amount of transition metal ions, and the transition metal is iron and manganese.
The preparation method of the double-carbon modified ferro-manganese-based mixed phosphate microsphere comprises the following steps:
1) Completely dissolving a carbon source in deionized water to obtain a carbon source solution;
2) Adding a sodium source and a phosphorus source into the carbon source solution obtained in the step 1), and completely dissolving;
3) Adding an iron source and a manganese source into the mixed solution obtained in the step 2), and stirring until a transparent clear solution is formed;
4) Adding the single-layer graphene oxide dispersion liquid into the mixed solution obtained in the step 3), and carrying out ultrasonic treatment and stirring to obtain a uniformly mixed solution;
5) Granulating the solution obtained in the step 4) by using a spray dryer to form a precursor, and calcining to obtain the double-carbon modified ferro-manganese-based mixed phosphate microsphere material.
According to the scheme, in the step 1), the addition amount of the carbon source is 1-1.5 times of the total molar amount of the transition metal ions, and the transition metal is iron and manganese.
According to the above scheme, in the step 1), the carbon source is citric acid, glucose or sucrose.
According to the scheme, in the step 2), the sodium source is sodium carbonate, sodium acetate or sodium dihydrogen phosphate; the phosphorus source is ammonium dihydrogen phosphate solid, diammonium hydrogen phosphate solid or sodium dihydrogen phosphate solid.
According to the scheme, in the step 3), the iron source is ferric nitrate nonahydrate solid or ferric acetate solid; the manganese source is manganese acetate solid or manganese acetate solid.
According to the above scheme, in the steps 2) and 3), the sodium source, the phosphorus source, the iron source and the manganese source are fed according to the stoichiometric ratio in the chemical formula.
According to the scheme, in the step 4), the addition amount of the single-layer graphene oxide is 2-5% of the mass of the target product; the target product is a double-carbon modified ferro-manganese-based mixed phosphate microsphere material.
According to the scheme, in the step 4), the ultrasonic time is 2-3h, and the stirring time is 6-12h.
According to the scheme, in the step 5), the granulating process conditions of the spray dryer are as follows: the spray drying temperature is 160-220 ℃, the circulating air flow is 80-90%, and the sample injection pump is 3-8%; the calcination process conditions are as follows: the calcination temperature is 550-600 ℃, the calcination time is 8-10 hours, the calcination atmosphere is argon-hydrogen mixed gas, and the heating rate is 2-5 ℃/min.
The application of the double-carbon modified ferro-manganese-based mixed phosphate microsphere material as a positive electrode active material of a sodium ion battery is provided.
The beneficial effects of the invention are as follows:
1. the invention provides a double-carbon-modified ferromanganese-based mixed phosphate microsphere material, on one hand, the specific surface area of the material is greatly improved by adopting a layered graphene and carbon co-modified microsphere structure, and the ferromanganese-based mixed sodium pyrophosphate microsphere coated by a graphene net and connected with a carbon layer is beneficial to increasing the conductivity of the material and improving the electrochemical performance; on the other hand, the introduction of Mn improves the operation potential, but easily causes reversible structural distortion to influence the stability of the material, and the existence of Fe can stabilize the material structure, and meanwhile, a firm mixed phosphate frame can adapt to the structural instability caused by Mn ions, so that the obtained microsphere material has good structural stability; at the same time study Na by theoretical calculation + The diffusion kinetics of the mixed phosphate frames obtained in the present invention was confirmed by Na + Diffusion can be performed in 3D channels with a low energy barrier; when the obtained microsphere material is used as a positive electrode material of a sodium ion battery, the cycling stability of the material is ensured, the working voltage is effectively improved, and the microsphere material has high reversible specific capacity, good cycling stability and excellent multiplying power performance.
2. The preparation method is simple, the required raw materials are green, safe, low in cost and easy to obtain, the method is simple, the yield is high, the uniformity of the product is good, and the market popularization is facilitated.
Drawings
FIG. 1 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) XRD pattern of the microsphere material.
FIG. 2 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) TG plot of microsphere material.
FIG. 3 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) SEM image of the microsphere nanomaterial. Wherein: FIG. 3a is a lower magnification of double carbon modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) A morphology map of the microsphere material; 3b is Na modified by double carbon at higher times 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) A morphology map of the microsphere material; 3c is Na modified by single carbon at a lower multiple 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Is a topography of (a); 3d is Na modified by single carbon at higher times 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Is a topography of the model (c).
FIG. 4 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Nitrogen isothermal adsorption and desorption curve graph of microsphere material.
FIG. 5 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) TEM image of microsphere nanomaterials. Wherein FIG. 5a is a double carbon modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) A transmission electron microscope image of the microsphere material; 5b is double carbon modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Lattice fringe patterns of the microsphere material under a high-resolution transmission electron microscope; 5c is single carbon modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Is a transmission electron microscope image; 5d is single carbon modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Lattice fringe pattern under high resolution transmission electron microscopy.
FIG. 6 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Charge-discharge curve graphs of microsphere materials at different current densities.
FIG. 7 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) And a micrometer sphere nano material multiplying power performance diagram.
FIG. 8 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Cycle contrast plot of microsphere nanomaterials at 0.5C (1c=129 mAh/g, the same applies below).
FIG. 9 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Cycling performance graph of microsphere material at 1C.
FIG. 10 shows a double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Cycling performance graph of microsphere material at 10C.
Detailed Description
For a better understanding of the invention, two experiments for coating different substances are performed in conjunction with the specific examples, and the results of the two experiments are compared to further illustrate the invention, but the invention is not limited to the following examples.
Example 1:
provides a double-carbon modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The preparation method of the microsphere comprises the following steps:
1) 18mmol of citric acid solids was added to 150ml of deionized water and completely dissolved to form a citric acid solution.
2) 20mmol of ammonium dihydrogen phosphate solid and 20mmol of sodium acetate powder were added to the citric acid solution and dissolved well.
3) 7.5mmol of ferric nitrate nonahydrate powder and 7.5mmol of manganese acetate tetrahydrate solid are added into the solution obtained in the step 2) in sequence, and the mixture is stirred for 5 hours to form a clear and transparent solution.
4) 100mg (concentration of 2 mg/mL) of monolayer redox graphene dispersion liquid is added into the solution obtained in the step 3), and the mixed solution is subjected to ultrasonic treatment for 3 hours and then stirred for 12 hours.
5) And (3) spray drying the solution obtained in the step (4), wherein the spray drying temperature is 180 ℃, the circulating air flow is 90%, the sample injection pump is 5%, placing the obtained precursor into a tube furnace for calcination, the calcination temperature is 550 ℃, the calcination time is 10 hours, the calcination atmosphere is argon-hydrogen mixed gas, and the heating rate is 2 ℃/min. The final calcined product is double-carbon modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microspheres (labeled NFMPP-rGO).
The material can be used as a positive electrode material of a sodium ion battery to realize the reversible discharge capacity of 120.56mAh g -1 The average operating potential was 3.24V, with excellent cycling stability at different current densities.
Comparative example 1:
the procedure was as in example 1, except that 100mg of the redox graphene dispersion was not added in step 4) to obtain single carbon layer modified Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) (labeled NFMPP).
Double carbon modified Na with the product obtained in example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere and single carbon layer modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The microspheres are used as examples, and performance tests are carried out, and the results are as follows:
as determined by an X-ray diffractometer, as shown in fig. 1, the X-ray diffraction pattern (XRD) showed that the peak positions of the microspheres obtained in example 1 and comparative example 1 were substantially identical.
FIG. 2 shows the results of thermogravimetric analysis of the two carbon modified Na obtained in example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The carbon content of the microspheres was 11.53%, and the single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The carbon content of the microspheres was 7.2%. And a proper amount of carbon is coated on the surface of the material, so that the diffusion of ions and the conductivity of the material are improved, and the capacity of the electrode material is improved to a great extent.
FIG. 3 Scanning Electron Microscope (SEM) shows that the dual carbon modified Na obtained in example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Single carbon modified Na obtained in comparative example 1 of microsphere surface 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The microsphere roughness is formed by coating a stacked graphene sheet network on the surface.
FIG. 4 shows the isothermal adsorption and desorption curves of nitrogen gas for the two-carbon modified Na obtained in example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Specific surface area comparison of microspheresSingle carbon modified Na obtained in example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The high microsphere is beneficial to improving the probability of the active material contacting the electrolyte, thereby improving the performance of the battery.
Fig. 5 shows the results of high resolution Transmission Electron Microscopy (TEM) tests of the products obtained in the examples and comparative examples, wherein fig. 5a and 5c are transmission electron microscopy images of the examples and comparative examples, respectively, both of which are solid spheres. Fig. 5b and 5d are high resolution transmission electron micrographs of examples and comparative examples, respectively, both having good crystallinity, in which the presence of a single layer of graphene is observed on the surface of the sample obtained in the examples, and the graphene network connects the microspheres to each other, facilitating electron transport.
Double carbon modified Na obtained in example 1 of the present invention 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The microsphere material is used as a positive electrode active material of the sodium ion battery, and the rest steps of the preparation method of the positive electrode material are the same as those of the common preparation method. The preparation method comprises the following steps:
respectively using the two-carbon modified Na obtained in example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) Microsphere material and single carbon modified Na obtained in comparative example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The microsphere material is used as an active material, acetylene black is used as a conductive agent, PVDF is used as a binder, and the mass ratio of the active material to the acetylene black to the polytetrafluoroethylene is 70:20:10; fully mixing the components according to the proportion, adding a small amount of NMP, carrying out ultrasonic homogenization, and coating on an aluminum foil with the thickness of 2mm to serve as an electrode plate of a sodium ion battery; and (5) placing the coated positive electrode plate in a vacuum oven at 70 ℃ for drying for 24 hours for later use. EC: DEC: FEC (20:20:1) is used as electrolyte, sodium sheets are used as cathodes, GF/D glass fibers are used as diaphragms, and two groups of sodium ions are assembled with 2016 anode and cathode battery shells in a glove box filled with argon gasA button cell.
After electrochemical performance testing, the dual carbon modified Na obtained in example 1 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 ) The microsphere material is subjected to constant-current charge-discharge test at 0.1C, and has a discharge specific capacity of 121mAh/g, and a capacity retention rate of 81.82% after 500 charge-discharge cycles at 1C current density. At a current density of 10C, the capacity retention rate was 86.4% after 7000 charge-discharge cycles.
Claims (10)
1. The double-carbon modified ferromanganese-based mixed phosphate microsphere material is characterized by comprising ferromanganese-based mixed sodium pyrophosphate microspheres coated by a carbon layer and reduced graphene oxide; wherein, the reduced graphene oxide network is coated and connected with the ferromanganese-based mixed sodium pyrophosphate microspheres coated by the carbon layer; the chemical formula of the ferromanganese-based mixed sodium pyrophosphate phosphate is Na 4 Fe 1.5 Mn 1.5 (PO 4 ) 2 (P 2 O 7 )。
2. The dual-carbon modified ferro-manganese-based mixed phosphate microsphere material according to claim 1, wherein the dual-carbon modified ferro-manganese-based mixed phosphate microsphere material has a diameter of 1-10 μm.
3. The dual-carbon modified ferro-manganese-based mixed phosphate microsphere material according to claim 1, wherein the carbon content in the dual-carbon modified ferro-manganese-based mixed phosphate microsphere material is 10-13%.
4. The double-carbon-modified ferro-manganese-based mixed phosphate microsphere material according to claim 1, wherein the addition amount of raw material single-layer graphene oxide of reduced graphene oxide is 2-5% of the mass of the double-carbon-modified ferro-manganese-based mixed phosphate microsphere material; the carbon source addition amount of the carbon coating layer is 1-1.5 times of the total molar amount of transition metal ions, and the transition metal is iron and manganese.
5. A method for preparing the double-carbon modified ferro-manganese-based mixed phosphate microspheres according to any one of claims 1-4, comprising the steps of:
1) Completely dissolving a carbon source in deionized water to obtain a carbon source solution;
2) Adding a sodium source and a phosphorus source into the carbon source solution obtained in the step 1), and completely dissolving;
3) Adding an iron source and a manganese source into the mixed solution obtained in the step 2), and stirring until a transparent clear solution is formed;
4) Adding the single-layer graphene oxide dispersion liquid into the mixed solution obtained in the step 3), and carrying out ultrasonic treatment and stirring to obtain a uniformly mixed solution;
5) Granulating the solution obtained in the step 4) by using a spray dryer to form a precursor, and calcining to obtain the double-carbon modified ferro-manganese-based mixed phosphate microsphere material.
6. The method according to claim 5, wherein in the step 1), the carbon source is added in an amount 1 to 1.5 times the total molar amount of the transition metal ions, and the transition metal is iron and manganese; in the step 4), the addition amount of the single-layer graphene oxide is 2-5% of the mass of the target product.
7. The method according to claim 5, wherein,
in the step 1), the carbon source is citric acid, glucose or sucrose;
in the step 2), the sodium source is sodium carbonate, sodium acetate or sodium dihydrogen phosphate; the phosphorus source is ammonium dihydrogen phosphate solid, diammonium hydrogen phosphate solid or sodium dihydrogen phosphate solid;
in the step 3), the iron source is ferric nitrate nonahydrate solid or ferric acetate solid; the manganese source is manganese acetate solid or manganese acetate solid.
8. The method according to claim 5, wherein in the steps 2) and 3), the sodium source, the phosphorus source, the iron source and the manganese source are added according to the stoichiometric ratio in the chemical formula.
9. The method according to claim 5, wherein,
in the step 4), the ultrasonic time is 2-3h, and the stirring time is 6-12h;
in the step 5), the granulation process conditions of the spray dryer are as follows: the spray drying temperature is 160-220 ℃, the circulating air flow is 80-90%, and the sample injection pump is 3-8%; the calcination process conditions are as follows: the calcination temperature is 550-600 ℃, the calcination time is 8-10 hours, the calcination atmosphere is argon-hydrogen mixed gas, and the heating rate is 2-5 ℃/min.
10. The use of the dual carbon modified iron-manganese based mixed phosphate microsphere material according to any one of claims 1-4 as a positive electrode active material of a sodium ion battery.
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